EP1721689B1 - Processus de production d'un article coulé - Google Patents

Processus de production d'un article coulé Download PDF

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Publication number
EP1721689B1
EP1721689B1 EP05710586A EP05710586A EP1721689B1 EP 1721689 B1 EP1721689 B1 EP 1721689B1 EP 05710586 A EP05710586 A EP 05710586A EP 05710586 A EP05710586 A EP 05710586A EP 1721689 B1 EP1721689 B1 EP 1721689B1
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EP
European Patent Office
Prior art keywords
mold
mixture
casting process
cast article
recited
Prior art date
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Active
Application number
EP05710586A
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German (de)
English (en)
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EP1721689A1 (fr
EP1721689A4 (fr
Inventor
Yusuke c/o Sintokogio Ltd. KATO
Toshihiko c/o Sintokogio Ltd. ZENPO
Norihiro c/o Sintokogio Ltd. ASANO
Masahiko c/o Sintokogio Ltd. NAGASAKA
Kazuyuki c/o Sintokogio Ltd. Nishikawa
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Sintokogio Ltd
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Sintokogio Ltd
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Publication of EP1721689A4 publication Critical patent/EP1721689A4/fr
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22CFOUNDRY MOULDING
    • B22C1/00Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/02Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by additives for special purposes, e.g. indicators, breakdown additives
    • B22C1/10Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by additives for special purposes, e.g. indicators, breakdown additives for influencing the hardening tendency of the mould material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22CFOUNDRY MOULDING
    • B22C1/00Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
    • B22C1/18Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of inorganic agents
    • B22C1/186Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of inorganic agents contaming ammonium or metal silicates, silica sols
    • B22C1/188Alkali metal silicates
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22CFOUNDRY MOULDING
    • B22C9/00Moulds or cores; Moulding processes
    • B22C9/02Sand moulds or like moulds for shaped castings
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22CFOUNDRY MOULDING
    • B22C9/00Moulds or cores; Moulding processes
    • B22C9/10Cores; Manufacture or installation of cores
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D29/00Removing castings from moulds, not restricted to casting processes covered by a single main group; Removing cores; Handling ingots
    • B22D29/001Removing cores
    • B22D29/005Removing cores by vibrating or hammering

Definitions

  • This invention relates to a casting process, more particularly, to a casting process that is capable of substituting for the conventional shell mold process and capable of readily removing a mold.
  • a shell mold process is known as disclosed in Japanese Patent Early-Publication No. 5-261478 .
  • the shell mold process employs a binder that includes a phenol-formaldehyde resin. Molding sand that is coated with such a binder is charged into a heated mold using a blowing introducing process. The coating binder of the charged molding sand is then hardened by the heat transferred from the mold.
  • a core mold that is poured and molded has a higher hardness. This needs a core-knockout process to apply greater impact forces to the core mold to collapse or crush it to remove it from a cast article.
  • the cast article should be sufficiently cooled before it is heat treated. As much as 70-80% of the sand grains can be removed from the cast article when the relatively high impact forces of not less than 1MPa at an operating frequency as high as 10Hz or more are applied for 10 seconds or more. Consequently, the resulting collapsed or crushed core mold causes the residues of its sand grains (core-sand grains) or crushed rocks to remain in the cast article during the heat treatment of it and the following processes. Therefore, the process of removing the residues may be needed once again. To recycle and use recovered residues of the collapsed core mold from the cast article, a roasting process is generally required to achieve this purpose.
  • the binder In the shell mold process, the binder generates volatile gases when it is to be hardened by the heat transferred from the mold.
  • the volatile gases involve unpleasant odors.
  • the phenol-formaldehyde, phenol, and ammonium gases impose a biohazard for humans.
  • a pourable foundry molding compositions which comprise refractory filler material, water, a bonding agent and a foaming agent selected from the class of anionic alcohol sulphate foaming agents such that it produces a foam structure in the composition of an inherently limited life ensuring dispersion of the foam shortly after pouring.
  • GB 1 361 027 and CH 470 922 disclose casting molds using a self-hardening material.
  • an aggregate granular material means that it comprises one or more of silica, zircon, sand, olivine sand, chromite sand, mullite, artificial sand, and so forth.
  • the term "after a molten metal is solidified" or "the solidified molten metal” refers to the molten metal being solidified and hardened.
  • the temperatures at which the molten metal can be solidified and hardened are various, and depend on the kinds of the processes and the materials of the molten metal.
  • the term “during a cooling process of a cast article” refers to the period to cool the cast article to lower the temperature until the cast article is cooled enough to cause no deformation of it when it is removed from the completed mold.
  • the term “during a cooling process of the cast article” refers to the period to cool the cast article lower than about the 520 deg. C used for a typical solution treatment, but higher than the conventional cooling range from 70 deg. C to 111 deg. C, such as the period to cool the cast article at temperatures down to 300 deg. C.
  • One aspect of the present invention provides a casting process.
  • the process comprises the steps of:
  • the mold that is cast in the hardened mixture is a core mold.
  • a mating mold i.e., a master mold, may be a metal mold or a sand mold.
  • a complete mold refers to an assembly that is assembled from the master mold with at least one molding mold, i.e., the core mold.
  • Such an assembly refers to a mold for which the molten metal can be poured.
  • the complete mold may include any element required for the pouring process, as well as the master mold and the core mold.
  • the casting process of the present invention may further comprise the steps of returning the aggregate granular material, and recovering the returned aggregate granular material.
  • the returned and recovered aggregate granular material is preferably recycled and used for molding a mold.
  • the steps of returning and recovering the aggregate granular material are mechanical recovering processes.
  • the cast article may be cast in an aluminum alloy, a magnesium alloy, a copper alloy, and so forth.
  • the heat treatment may be the T6 treatment or the T7 treatment.
  • the step of removing the completed mold from the cast article is to shake the completed mold.
  • it includes impact forces of less than 1MPa at an operating frequency at less than 30Hz being applied in the completed mold for less than 30 seconds, within from 5 to 20 minutes after the molten metal is poured.
  • Fig. 1 is a flowchart that schematically shows the steps of the casting process of the present invention. The principles of the casting process of the present invention will now be described in line with the flowchart of Fig. 1 .
  • a first step one or more kind of aggregate granular material, one or more kind of a water-soluble binder, and water are mixed to form a mixture of the aggregate granular material.
  • the resulting mixture is then stirred to cause it to foam (the first or preparing step 1).
  • the foamed mixture obtained in the first step is charged into a molding space.
  • the moisture within the charged mixture is then evaporated to harden the charged mixture to mold a mold with the hardened mixture, i.e., the aggregate granular material (the second or molding step 2).
  • a third step at least one mold (a core mold) that is cast in the hardened mixture is assembled with a mating mold (a master mold) to form a completed mold (the third or assembling step 3).
  • a molten metal is poured into the completed mold (the fourth or pouring step 4).
  • the core mold is removed ("core out") from a cast article that is composed of the solidified molten metal to disassemble the completed mold during a process of cooling the cast article after the molten metal is solidified (the fifth or disassembling step 5).
  • a heat treatment is applied to the cast article (the sixth or heat treatment step 6).
  • the resulting completed cast article is thus produced.
  • the aggregate granular material comprises one or more materials made of silica, zircon, sand, olivine sand, chromite sand, mullite, artificial sand, and so forth.
  • a desirable water-soluble binder has water-solubility at room temperature.
  • the water-soluble binder having the water-solubility at room temperature can be formed into the aggregate granular material without heating. This can save the energy and time required for heating the binder and the aggregate granular material that would otherwise be required.
  • This advantage of the present invention is significantly contrasted with the prior-art production of coated sand in the conventional shell molding process.
  • a suitable water-soluble binder is a polyvinyl alcohol or its derivative, or a starch or its derivative, or both. Because the water-soluble binder can be readily evaporated or dissolved, the core mold can be readily removed from the cast article in which the molten metal has been solidified in the fifth disassembling step 5.
  • the aggregate granular material preferably contains the water-soluble binder from 0.1 to 5.0 wt% based on the total weight of the aggregate granular material.
  • One or more kind of the water-soluble binder and one or more kind of the aggregate granular material and water are mixed to form a mixture of the aggregate granular material.
  • the mixture of the aggregate granular material is stirred to cause it to foam and thus it is formed as a whipped cream mixture.
  • the foamed mixture is charged into the molding space, and the moisture within the charged mixture is then evaporated to harden the charged mixture to mold a core mold.
  • This core mold has a hollow structure due to the foam within the aggregate granular material.
  • the hollow core mold has a porosity of 3 to 60 %. For example, if the hollow core mold is about 40 mm in thickness, more than 50% of a water-soluble binder is aggregated in the surface layer between the surface of the core mold and a depth of 10 mm therefrom.
  • the distribution of the foam in the aggregate granular material and the moisture content of the binder are concentrated at the center portion of the core mold. After the moisture is evaporated, the center portion of the core mold has thus a low density of the charged aggregate granular material.
  • the master mold may be a metal mold or a sand mold that is composed of, e.g., the aggregate granular material.
  • the master mold is a metal mold
  • the casting process is a low-pressure casting. If the master mold is a metal mold, the casting process of the present invention is not limited to the low-pressure casting, but may be applied to a back-pressure casting, a die-casting, or a gravitational casting for casting the metal mold and so forth.
  • the embodiment employs, without limitation, an aluminum alloy as the molten metal to be poured into the completed mold.
  • an aluminum alloy as the molten metal to be poured into the completed mold.
  • other materials including a light metal alloy or a nonferrous alloy (e.g., a magnesium alloy or a copper alloy) may be used.
  • a cast iron, a cast steel, or an iron metal alloy may be used. If the iron metal alloy is used as the molten metal, a mold wash or a facing material may be desirably applied on the core mold.
  • the core mold is removed from the cast article during the periods for a process to cool the cast article or the period to cool the cast article and lower the temperature until the cast article is cooled enough to cause no deformation of it when it is removed from the completed mold.
  • the material of the molten metal in the fourth or pouring step 4 is an aluminum alloy
  • the term "during the periods of a cooling process of the cast article” refers to the period to cool the cast article lower than about the 520 °C used in the solution treatment, but higher than the conventional cooling range from 70 to 111°C, such as the period to cool the cast article at a temperatures down to 300 °C.
  • the heat treatment is the T6 treatment or the T7 treatment and so forth.
  • the heat treatment step 6 of the casting process of the present invention may be followed by additional steps, if needed.
  • the additional steps include a step 7 of returning the used aggregate granular material (i.e., the core-sand grains) or crushed rocks, a step 8 of milling the crushed rocks, and a step 9 of mechanically recovering the returned sand grains.
  • the returned and recovered sand grains can be recycled and used for molding a new core mold.
  • the prior-art shell molding process needs heating elements for the production of the resin-coated sand and needs deodorizing equipment for removing the hazardous gases due to heating the resin.
  • the preparing step 1 needs neither a heating element nor deodorizing equipment.
  • Two whipped and creamy mixtures, A and B, that are prepared in the preparing step 1, are separately pressure-charged into a respective cavity (not shown) in the corresponding metal mold (not shown), which is maintained at a temperature of 250 °C, and held for a period of one minute.
  • the moisture content within the respective mixture is evaporated to harden the mixture such that a respective core mold is removed from a respective cavity of the corresponding metal mold (the molding step 2).
  • the core mold is assembled with the mating mold to form the completed mold (the assembling step 3).
  • the respective core mold and the corresponding master metal mold of a low-pressure molding machine are assembled to form the completed mold so that it is ready and waiting for the pouring step.
  • the molten metal is poured into the respective completed mold (the pouring step 4).
  • a molten metal of an aluminum metal alloy AC4C having a temperature of 720 °C is poured from beneath into the respective completed mold using the low-pressure molding machine (not shown). With the temperature of 720 °C of the molten metal, the binder can be volatilized or dissolved such that the respective core molds can be readily removed from the corresponding cast article in the following step.
  • the respective core mold is removed from the corresponding cast article during the periods of a cooling process of the cast article after the molten metal is solidified (the removing step 5).
  • the prior-art shell mold process needs a process to apply a greater impact to the core mold to collapse it to remove it from the cast article that has been sufficiently cooled.
  • the core mold does not need either significant cooling nor a following step to apply a high impact force on it to remove it from the cast article. Accordingly, the core mold can be easily removed from the cast article such as by means of weak shakings, described below.
  • the cast article that is composed of the solidified molten metal is removed from the completed mold 10 minutes after the pouring is completed.
  • the weak shakings or the impact forces of less than 1MPa at an operating frequency of 20Hz are applied to the cast article having a temperature of 350°C for less than 20 seconds to remove sand particles such that the core mold is completely removed from the cast article.
  • the weak shakings or the impact forces of less than 1MPa at an operating frequency of less than 30 Hz are continued in periods of less than 30 seconds, within from 5 to 20 minutes after said molten metal is poured.
  • the core mold can be also completely removed from the cast article.
  • the cast article is heat-treated (the heat treatment step 6) after its pouring gate and casting fines are removed.
  • the pouring gate and casting fines of the cast article are removed before the heat treatment step, they may be removed after the heat treatment step.
  • the heat treatment step 6 of this embodiment may be followed by the returning step 7, the milling step 8, and the mechanical recovery step 110, as shown in Fig. 1 .
  • the used aggregate grains or crushed rocks are salvaged or returned from just the core mold and thus the salvaged and recovered aggregate grains may be readily recycled and used for molding a new mold.
  • Fig. 2 shows a comparative flowchart of the prior-art casting processes based on the shell molding process as disclosed in Japanese Patent Early-Publication No. 5-261478 .
  • the prior-art process of Fig. 2 employs resin-coated sand.
  • the resin-coated sand is prepared and commercially delivered from a manufacturer that differs from a castings industry maker. Therefore, a step 11 of preparing the coated-sand is typically carried out at a site that differs from casting facilities. This causes difficulties in recycling and using the used resin-coated resin for molding a mold, even if the used resin coated resin may be successfully salvaged and recovered. This contrasts with the casting process of the present invention.
  • the castings industry maker heats the commercially available resin-coated sand to mold a core mold (as shown in a step 12), and assembles it with another mold into a completed mold (as shown in a step 13). Then the molten metal is poured into the completed mold (as shown in a step 14). The core mold is then removed or shaken out from the cast article with a furnace for removing sand (as shown in a step 15). After the cast article is sufficiently cooled (as shown in a step 16) the molded sand should be completely shaken out by using the knockout process (as shown in a step 17).
  • the cast article is then subjected to the heat treatment (as shown in a step 18).
  • the core sand that includes sand clots is returned (as shown in a step 19).
  • the returned sand is milled (as shown in a step 20), roasted (as shown in a step 21), and mechanically recovered (as shown in a step 22) by a company that produces resin-coated sand.
  • a company mostly does the production away from the job site of the returning step 19.
  • the number of processes in the casting process of the present invention as shown in Fig. 1 is lower than the number of the prior-art processes as shown in Fig. 2 .
  • the removing step 5 of the inventive casting process of the present invention can be readily carried out with a means for removing the sand such as a means using weaker shakings, since the inventive casting process employs the collapse-prone core molds.
  • the prior-art casting process as shown in Fig. 2 needs the removing step 15 for removing the sand by means of the furnace for removing sand, the cooling step 16 for sufficiently cooling the cast article, and the knockout process 17.
  • the inventive casting process needs no roasting process 21 for returning and recovering the used sand as in the prior-art casting process.
  • Fig. 3 is a graphic representation of the relationships between the temperatures of the cast article and the periods during the step 5 to remove a completed mold from the cast article and the process 6 to apply the heat treatment to the cast article of the embodiment of the present invention.
  • Fig. 4 is also a graphic representation similar to Fig. 3 , but for the corresponding steps of the prior-art process.
  • the prior-art process there is a sufficient cooling of the cast article (the step 16 of Fig. 2 ) followed by removing the sand with a knockout process (the step 17 of Fig. 2 ).
  • the cast article is then re-heated to subject it to the T6 treatment.
  • the prior-art process thus needs the time to cool the cast article, the time to re-heat the cast article to subject it to the heat treatment, and consumes energy.
  • the molten metal having a temperature of 720°C is poured into the completed mold.
  • the cast article that is composed of the solidified molten metal is then removed from the completed mold followed by the core mold being removed from the cast article.
  • the cast article needs no greater impact force to be applied to it after it is sufficiently cooled.
  • the cast article thus can be immediately subjected to the heat treatment. This causes a reduction of the time to cool the cast article, the time to re-heat it for the heat treatment, the consumption of energy, and the number of processes. When consuming energy, it is not necessary to cool the cast article at temperatures down to 100 °C, or even to cool the cast article to a temperature down to 300 °C.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Molds, Cores, And Manufacturing Methods Thereof (AREA)
  • Mold Materials And Core Materials (AREA)
  • Glass Compositions (AREA)

Claims (13)

  1. Procédé de coulée comprenant les étapes de :
    - mélange d'un ou plusieurs types d'un matériau granulaire agrégé, d'un ou plusieurs types d'un liant soluble dans l'eau et d'eau, pour former un mélange dudit matériau granulaire agrégé, et agitation dudit mélange pour faire en sorte qu'il mousse ;
    - chargement dudit mélange moussant dans un espace de moulage, et évaporation de l'humidité au sein dudit mélange chargé pour durcir ledit mélange chargé pour mouler un moule avec ledit mélange durci ;
    - assemblage d'au moins un moule qui est coulé dans ledit mélange durci et du moule correspondant pour former un moule complet ;
    - déversement de métal en fusion dans ledit moule complet ;
    - enlèvement dudit moule complet d'un article coulé qui est composé du métal en fusion solidifié lors d'un processus de refroidissement dudit article coulé après que ledit métal en fusion s'est solidifié ; et
    - application d'un traitement thermique audit article coulé,
    caractérisé en ce que ledit un ou lesdits plusieurs types dudit liant soluble dans l'eau est ou sont au moins un poly(alcool vinyliqùe) ou son dérivé, ou au moins un amidon ou son dérivé.
  2. Procédé de coulée selon la revendication 1,
    dans lequel ledit au moins un moule qui est coulé dans ledit mélange durci est un coeur, et ledit moule correspondant est un moule maître.
  3. Procédé de coulée selon la revendication 2,
    dans lequel ledit moule maître est un moule en métal.
  4. Procédé de coulée selon la revendication 2,
    dans lequel ledit moule maître est un moule en sable.
  5. Procédé de coulée selon l'une quelconque des revendications précédentes,
    comprenant en outre des étapes de retour dudit matériau granulaire agrégé, et de récupération dudit matériau granulaire agrégé retourné.
  6. Procédé de coulée selon la revendication 5,
    comprenant en outre des étapes de recyclage et d'utilisation dudit matériau granulaire agrégé retourné et récupéré pour mouler un moule.
  7. Procédé de coulée selon la revendication 5 ou 6,
    dans lequel lesdites étapes de retour et de récupération dudit matériau granulaire agrégé sont des processus de récupération mécaniques.
  8. Procédé de coulée selon l'une quelconque des revendications précédentes,
    dans lequel ledit article coulé est coulé dans un alliage d'aluminium ou un alliage de magnésium.
  9. Procédé de coulée selon la revendication 8,
    dans lequel ledit traitement thermique est un traitement T6 ou un traitement T7.
  10. Procédé de coulée selon l'une quelconque des revendications 1 à 7,
    dans lequel ledit article coulé est coulé dans une fonte de coulée, un acier de coulée ou un alliage ferreux.
  11. Procédé de coulée selon l'une quelconque des revendications 1 à 7,
    dans lequel ledit article coulé est coulé dans un alliage de cuivre.
  12. Procédé de coulée selon l'une quelconque des revendications 1 à 7,
    dans lequel ladite étape d'enlèvement dudit moule complet dudit article coulé consiste à appliquer des secousses dans ledit moule.
  13. Procédé de coulée selon l'une quelconque des revendications 1 à 7,
    dans lequel ladite étape d'application desdites secousses dans ledit moule inclut des forces d'impact de moins de 1 MPa à une fréquence opérationnelle de moins de 30 Hz étant appliquées dans ledit moule pendant moins de 30 secondes, dans une plage de 5 à 20 minutes après que ledit métal en fusion a été déversé.
EP05710586A 2004-02-25 2005-02-23 Processus de production d'un article coulé Active EP1721689B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2004049428 2004-02-25
PCT/JP2005/002893 WO2005080023A1 (fr) 2004-02-25 2005-02-23 Processus de production d’un article coulé

Publications (3)

Publication Number Publication Date
EP1721689A1 EP1721689A1 (fr) 2006-11-15
EP1721689A4 EP1721689A4 (fr) 2007-05-02
EP1721689B1 true EP1721689B1 (fr) 2011-05-18

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US (1) US20070137825A1 (fr)
EP (1) EP1721689B1 (fr)
JP (1) JP3948490B2 (fr)
CN (1) CN1921969B (fr)
AT (1) ATE509714T1 (fr)
TW (1) TW200533436A (fr)
WO (1) WO2005080023A1 (fr)

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US10371686B2 (en) 2012-11-15 2019-08-06 Heraeus EIectro-Nite International N.V. Detection device for molten metal
US9789533B2 (en) 2012-11-19 2017-10-17 Sintokogio, Ltd. Sand for casting mold, manufacturing method for sand casting-mold, and core for metal casting
CN103601465B (zh) * 2013-11-06 2015-04-29 安庆帝雅艺术品有限公司 一种铜器填充材料
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MX2019002260A (es) * 2016-08-31 2019-07-04 Asahi Yukizai Corp Metodo de fabricacion de molde de fundicion.
AT520370B1 (de) 2017-09-07 2020-08-15 Fill Gmbh Verfahren zur Herstellung eines gegossenen Werkstückes
DE102017131255A1 (de) * 2017-12-22 2019-06-27 HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung Verfahren zur Herstellung eines metallischen Gussstücks oder eines ausgehärteten Formteils unter Verwendung aliphatischer Polymere umfassend Hydroxygruppen
JP7309405B2 (ja) * 2018-03-30 2023-07-18 株式会社巴川製紙所 鋳型用砂型資材及び鋳型用の中子及び砂型材の製造方法
TWI789125B (zh) * 2021-11-19 2023-01-01 財團法人金屬工業研究發展中心 低壓鑄造金屬發泡系統及中間發泡裝置

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JPS57115942A (en) * 1981-01-06 1982-07-19 Sintokogio Ltd Method for forming mold
JPS5832540A (ja) * 1981-08-21 1983-02-25 Sintokogio Ltd ダイカスト用中子の製造方法
JPH05261478A (ja) * 1992-03-19 1993-10-12 Ube Ind Ltd 崩壊性砂中子の製造方法

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EP1721689A1 (fr) 2006-11-15
JP3948490B2 (ja) 2007-07-25
CN1921969B (zh) 2015-03-18
JPWO2005080023A1 (ja) 2007-10-25
US20070137825A1 (en) 2007-06-21
ATE509714T1 (de) 2011-06-15
EP1721689A4 (fr) 2007-05-02
WO2005080023A1 (fr) 2005-09-01
CN1921969A (zh) 2007-02-28
TW200533436A (en) 2005-10-16

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